Intermolecular Forces and

Liquids and Solids

Chapter 11

A phase is a homogeneous part of the system in contact with other parts of the system but separated from them by a well-defined boundary.

2 Phases

Solid phase - ice

Liquid phase - water

11.1

Intermolecular Forces

11.2

Intermolecular forces are attractive forces between molecules.

Intramolecular forces hold atoms together in a molecule.

Intermolecular vs Intramolecular

• 41 kJ to vaporize 1 mole of water (inter)

• 930 kJ to break all O-H bonds in 1 mole of water (intra)

Generally, intermolecular forces are much weaker than intramolecular forces.

“Measure” of intermolecular force

boiling point

melting point

Hvap

Hfus

Hsub

Types of Intermolecular Forces1. Hydrogen Bond (strongest)

11.2

The hydrogen bond is a special dipole-dipole interaction between the hydrogen atom in a polar N-H, O-H, or F-H bond and an electronegative O, N, or F atom. IT IS NOT A BOND.

A H…B A H…Aor

A & B are N, O, or F

Hydrogen Bond

11.2

Why is the hydrogen bond considered a “special” dipole-dipole interaction?

Decreasing molar massDecreasing boiling point

11.2

Types of Intermolecular Forces

2. Ion-Dipole Forces

Attractive forces between an ion and a polar molecule

11.2

Ion-Dipole Interaction

11.2

Types of Intermolecular Forces

3. Dipole-Dipole Forces

Attractive forces between polar molecules

Orientation of Polar Molecules in a Solid

11.2

Types of Intermolecular Forces4. Dispersion Forces – van der Walls forces/London forces (weakest)

Attractive forces that arise as a result of temporary dipoles induced in atoms or molecules

11.2

ion-induced dipole interaction

dipole-induced dipole interaction

Intermolecular Forces4. Dispersion Forces Continued

11.2

Polarizability is the ease with which the electron distribution in the atom or molecule can be distorted.

Polarizability increases with:

• greater number of electrons

• more diffuse electron cloud

Dispersion forces usually increase with molar mass.

SO

O

What type(s) of intermolecular forces exist between each of the following molecules?

HBrHBr is a polar molecule: dipole-dipole forces. There are also dispersion forces between HBr molecules.

CH4

CH4 is nonpolar: dispersion forces.

SO2

SO2 is a polar molecule: dipole-dipole forces. There are also dispersion forces between SO2 molecules.

11.2

Properties of Liquids

Surface tension is the amount of energy required to stretch or increase the surface of a liquid by a unit area.

Strong intermolecular

forces

High surface tension

11.3

Properties of Liquids

Cohesion is the intermolecular attraction between like molecules

11.3

Adhesion is an attraction between unlike molecules

Adhesion

Cohesion

attracted to glass

attracted to each other

Properties of Liquids

Viscosity is a measure of a fluid’s resistance to flow.

11.3

Strong intermolecular

forces

High viscosity

Maximum Density40C

Ice is less dense than water

Density of Water

11.3

Water is a Unique Substance

A crystalline solid possesses rigid and long-range order. In a crystalline solid, atoms, molecules or ions occupy specific (predictable) positions.

An amorphous solid does not possess a well-defined arrangement and long-range molecular order.

A unit cell is the basic repeating structural unit of a crystalline solid.

Unit Cell

latticepoint

Unit cells in 3 dimensions 11.4

At lattice points:

• Atoms

• Molecules

• Ions

11.4

11.4

Types of Crystals

Ionic Crystals – Ion-Ion interactions are the strongest (including the “intermolecular forces” (H bonding, etc.)

• Lattice points occupied by cations and anions• Held together by electrostatic attraction• Hard, brittle, high melting point• Poor conductor of heat and electricity

CsCl ZnS CaF2

11.6

Types of Crystals

Covalent Crystals – Stronger than IM forces but generally weaker than ion-ion

• Lattice points occupied by atoms• Held together by covalent bonds• Hard, high melting point• Poor conductor of heat and electricity

11.6diamond graphite

carbonatoms

Types of Crystals

Molecular Crystals• Lattice points occupied by molecules• Held together by intermolecular forces• Soft, low melting point• Poor conductor of heat and electricity

11.6

Types of Crystals

Metallic Crystals – Typically weaker than covalent, but can be in the low end of covalent

• Lattice points occupied by metal atoms• Held together by metallic bonds• Soft to hard, low to high melting point• Good conductors of heat and electricity

11.6

Cross Section of a Metallic Crystal

nucleus &inner shell e-

mobile “sea”of e-

An amorphous solid does not possess a well-defined arrangement and long-range molecular order.

A glass is an optically transparent fusion product of inorganic materials that has cooled to a rigid state without crystallizing

Crystallinequartz (SiO2)

Non-crystallinequartz glass 11.7

Types of Crystals

11.6

Chemistry In Action: High-Temperature Superconductors

E

vapo

ratio

nGreatest

Order

LeastOrder

11.8C

onde

nsat

ion

T2 > T1

The equilibrium vapor pressure is the vapor pressure measured when a dynamic equilibrium exists between condensation and evaporation

H2O (l) H2O (g)

Rate ofcondensation

Rate ofevaporation=

Dynamic Equilibrium

11.8

Molar heat of vaporization (Hvap) is the energy required to vaporize 1 mole of a liquid.

ln P = -Hvap

RT+ C

Clausius-Clapeyron EquationP = (equilibrium) vapor pressure

T = temperature (K)

R = gas constant (8.314 J/K•mol)

11.8

C = constant (depends on P & T)

The boiling point is the temperature at which the (equilibrium) vapor pressure of a liquid is equal to the external pressure.

The normal boiling point is the temperature at which a liquid boils when the external pressure is 1 atm.

11.8

The critical temperature (Tc) is the temperature above which the gas cannot be made to liquefy, no matter how great the applied pressure.

The critical pressure (Pc) is the minimum pressure that must be applied to bring about liquefaction at the critical temperature.

11.8

Mel

ting

11.8F

reez

ing

H2O (s) H2O (l)

The melting point of a solid or the freezing point of a liquid is the temperature at which the solid and liquid phases coexist in equilibrium

Molar heat of fusion (Hfus) is the energy required to melt 1 mole of a solid substance.

11.8

11.8

Sub

limat

ion

11.8

Dep

ositi

on

H2O (s) H2O (g)

Molar heat of sublimation (Hsub) is the energy required to sublime 1 mole of a solid.

Hsub = Hfus + Hvap

( Hess’s Law)

A phase diagram summarizes the conditions at which a substance exists as a solid, liquid, or gas.

The triple point is where all 3 phases meet.

Phase Diagram of Water

11.9

11.9

Where’s Waldo?Can you find…

The Triple Point?

Critical pressure?

Critical temperature?

Where fusion occurs?

Where vaporization occurs?

Melting point (at 1 atm)?

Boiling point(at 6 atm)?

Carbon Dioxide

11.9

Chemistry In Action: Liquid Crystals